Regeneration of alumina adsorbents by oxidation



Patented Dec. 28, 1948 REGENERATION F ALUMINA ADSORBENTS BY OXDJATION Knut A. Krieger, Philadelphia, and Heinz Heinemann, Upper Darby, Pa., assignors to Poroccl Corporation, Philadelphia, Pa., a corporation of Delaware No Drawing. Application July I, 1945, Serial No. 603,744

2 Claims. 1

the present invention relates to a method of regenerating spent adsorbents, particularly those which have been employed in the refining or conversion of hydrocarbons such as petroleum oils, waxes, gases, and the like.

An object of this invention is the regeneration of spent adsorbents containing adsorbed carbonaceous materials resulting from the treatment of hydrocarbon oils, and more particularly is this invention concerned with the regeneration of spent bauxite and spent activated alumina under conditions conducive to the preservation of useful life of such materials.

A further object of this invention is the regeneration of spent bauxite and spent activated alumina which has been used as a catalyst in the conversion of higher boiling hydrocarbon oils into motor fuel of the gasoline boiling range. However, it is to be understood that the method of this invention is also applicable in regeneration of spent bauxite and spent activated alumina which has been employed in the reforming of naphthas to increase their anti-knock value; or in the desulfurization or removal of gum and gum-forming constituents from hydrocarbon oils and gases; or in the isomerization, aromatization, alkylation, or polymerization of hydrocarbon oils or gases; or in various other uses in which these adsorbents become fouled with tarry or carbonaceous materials and thus lose their conversion or refining efficiency.

We have discovered that in the thermal regeneration of spent or partially spent alumina adsorbents under conditions conducive to the oxidation of adsorbed carbonaceous materials, the humidity or quantity of water in the regenerating gas, 1. e., airor other free-oxygen containing gas, is an important factor in determining the extent of recovery of adsorbent activity upon repeated regeneration. More particularly, we have found that bauxite thermally regenerated in the presence of substantially dry air has a conversion or refining efliciency considerably greater than that of the original bauxite or of spent bauxite which has been regenerated in the presence of moist or humid air. We have further found the spent activated alumina, when thermally regenerated in the presence of substantially dry air, will exhibit a slower rate of decrease in conversion or refining efficiency than spent activated alumina thermally regenerated in the presence of moist air. The bauxite adsorbents referred to herein are commercially available materials generally prepared by crushing bauxite ore, drying the crushed ore to about 30% by weight water content, and thereafter grinding and screening the dried material to desired particle size. For many purposes, thebauxite thus prepared is thereafter activated by heating at a temperature between 600 F. and 1200 F. to obtain a residual volatile matter or water content (V. M.) within the range of 0.1% to 10% by weight. The activated alumina adsorbents, on the other hand, are usually prepared from aluminum trihydrate from the Bayer process, such alumina scale being washed, dried, crushed, screened, and thermally activated more or less in the same manner as bauxite. Activated alumina and bauxite, while'not being equivalent for all purposes, both respond to the method of regeneration of our invention, particularly after use in the conversion or refining of hydrocarbon.

In accordance with the present invention, a spent alumina adsorbent containing adsorbed carbonaceous materials is subjected to regeneration by heating at an elevated temperature for a period of time sufiicient to remove a substantial portion of the carbonaceous materials, the spent alumina being intimately contacted with substantially dry air or other free-oxygen containing gas during the. heating step. By substantially dry air we mean air or other oxidizing gas having a moisture content of not more than 3 milligrams per liter of air when measured at F. and 760 mm. pressure. Air or other oxidizing gas which has been dried by passing through a commercial dehumidifying or drying plant, and which has a moisture content not in excess of that above stated is suitable for our purpose. Such dehumidifying or moisture-absorbing plants may utilize agents such as activated alumina, activated bauxite, silica gel, calcium chloride, or copper sulfate for producing substantially dry air.

We prefer to carry out our regeneration of the spent alumina adsorbents at a temperature between 900 F. and 1400 F.', very satisfactory results being obtained between 1050 F. and 1200 F., and in no case do we employ temperature so high as to cause sintering of the adsorbent particles. Dry gases other than air may be used in our regeneration, including oxygen, mixtures of air and oxygen or ozone, combustion 0r flue gases, and the like. The regeneration may be carried out by passing the spent alumina adsorbent through a heated tower or'kiln concurrent or countercurrent to a stream of dry oxidizing gas, the gas charged to the tower or kiln having a moisture content not greater than 3 milligrams per liter of gas when measured at 75 F. and

'ieo mm.

. 3' pressure. Alternatively, the spent alumina adbsorbent may be regenerated in the same vessel in which it was used for converting or refining hydrocarbons, provided such vessel is 4 the oil through a preheater to raise the temperature oi. the oil to about 850 F. and the resuiting oil and vapors were passed at. atmospheric pressure through a bed or adsorptive equipped with suitable means for controlling or 5 alumina catalyst contained in a heated reaction dissipating the heat of regeneration. In most vessel, the oil being charged at a rate of 1 volume cases it is desirable to remove from the spent per volume of catalyst per hour. The cracking alumina adsorbent a substantial portion or the temperature was maintained at 900 F. when adsorbed or mechanically held carbonaceous bauxite was used and at 975 F. when activated material such as oil. tar, or polymers, etc., prior alumina was used. The cracked products from to subjecting thealumina to thermal regenerathe reaction vessel were fractionated and a 400 tion. This may be accomplished by purging the F. end point gasoline fraction was separated, the spent alumina with a non-oxidizing gas at temquantity of such fraction being indicative of the peratures preferably not high than about 900 F. cracking efliciency oi the catalyst. The quantity Such gases include nitrogen, hydrogen, carbon of gasoline obtained with fresh catalyst in the monoxide, carbon dioxide, methane, ethane, and first cracking run was chosen to represent 100% the like. When steam is used to purge the spent efliciency, n the o para ive increase or dealumina, the temperature should be maintaned crease in efllciency upon repeated use an below about 700 F. and the alumina, after pur generation s ased upon this arbitrary initial ing, should be dried with air or other gas prior to V lueraising the temperature to the level required for The bauxites employed were obtained from regeneration, i. e., 900 F. to 1400" F. If this is various sources. Sample 1 was a m h not done, the full benefit of our improved regenkansas bauxite having a moisture content of 28%, eration method will not be realized, since the and which was heated in the reaction vessel in a presence of moisture has an adverse efiect at stream of nitrogen at 900 F. for 1 hour prior to regenerating temperatures. While it is generally the introduction of the oil to be cracked. Sample more economic to effect purging with a non- 2 Was a 9&1 mesh bauxite from Dutch Guiana oxidizing gas or with steam, such purging may which had been activated by heating at 900 F. also be efiected by treating the spent alumina to a moisture content of 6%. Sample 3 was anadsorbent with solvents such as methyl alcohol, 30 ot r Arkansas 914 mesh bauxite which had been ethyl alcohol, isopropyl alcohol, acetone, methyl activated y heating at 90 F. to a moisture conethyl ketone, benzene, toluene, naphtha gasoline, tent of 6%. The activated alumina was produced pyridine, or mixtures of .tWo or more thereof. y the Bayer process, and had a mesh size r 91 The solvent purging may be carried out at ordiand a moisture content f as Pu ased. nary or elevated temperatures below the decom- The above catalysts W re repeatedly used for position temperature of the solvent, and residual Cracking and were repeat y e d, using solvent may be removed prior to thermal regeny air o e t an 3 m igrams of water pe eration by sweeping the purged alumina adliter at 75 F. and 760 mm. pressure) on one hand, sorbent with air, inert gases, or steam. When and wet air (100% humidity at 75 F. or 22 millisteam is used, the adsorbent should be dried begrams of water p liter at 7 F. and 760 mm. low 700 F. before regeneration with dry air at pressure) on the other hand. After each crackhigher temperatures. It is to be understood, of ing run was completed, the reaction vessel was course, that purging with nonoxidizing gases, flushed with nitrogen for 1 hour to purge the steam, or solvents effects only a partial removal catalyst granules of oil vapors and a portion of of adsorbed oils, tars, or carbonaceous materials, .45 the adsorbed carbonaceous materials, and the oxiand that the thermal regeneration removes an dizing gas was then passed through the vessel for additional quantity of such materials. The 1 hourin intimate contact with the catalyst to alumina adsorbent, after regeneration, may still oxidize and remove an additional quantity of contain small amounts of carbon since it is almost carbonaceous materials, thereby regenerating the impossible to remove all carbonaceous material, cracking activity of the catalyst. During the reand the small residual carbon content, for all generation, the temperature was maintained at practical purposes, has little or no influence upon 1200 F. The temperature was then lowered to the conversion or refining efllciency of the re- 900 F. or 975 F. and cracking was resumed.

generated aumina adsorbent. The results obtained are given in the following Our invention may be further illustrated by the table, the terms dry air and wet air being following examples, which, however, are not to be used for brevity and comprehending the definiconstrued as limiting the scope thereof. 1 tions thereof above set, forth.

Catalyst Bauxite #1 Bauxite #2 Bauxite#3 Act. Alumina Cracking Temp 900 F. 900 F 900 F. 975 F.

Regenerating Temp 1,200 F. l,200 F. l,200 F. l,200 F.

RegeneratongAir dry wet dry wet dry wet dry wet Cracking Efliciency:

Fresh Catalyst 100 100 100 100 100 100 100 100 1st Regeneration 134 126 144 80 161 138 76 2nd Regeneration" 128 105 12s as 151 131 81 59 3rd Regeneratiom. 128 95 144 147 93 83 61 An East Texas gas oil having an A. P. I. gravity of 37 and a distillation range of 450 F. to 720 F. was employed in the cracking runs reported below. The cracking was carried out by passing and that the activities of the various catalysts From the above data, it will be apparent that regeneration with "dry air gives markedly improved results over regeneration with wet air,

difler considerably from one another. However, in all cases, the improvement in regeneration in accordance with the present invention is definitely established.

We claim:

1. A method of regenerating a spent alumina containing adsorbed carbonaceous materials,

which comprises purging said'spent alumina with steam to remove at least a portion of the carbonaceous materials, removing moisture resulting from the steaming of said purged alumina at a temperaturenot higher than 700 F., and then heating said purged alumina at a temperature between 900 F. and 1400 F. in a current of air carrying not more than 3 milligrams of water per liter 01' air measured at 75 F. and 760 mm. pressure for a period 01 time sufficient to remove an additional portion of said carbonaceous materials.

2. A method of regenerating spent bauxite containing adsorbed carbonaceous materials, which comprises purging said spent bauxite with steam to remove at least a portion of the carbonaceous REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,215,304 Voorhies, Jr Sept. 17, 1940 20 2,225,402 Liedholm Dec. 17, 1940 2,383,218 Schulze Aug. 21, 1945 

